Solvent extraction of naphthas



NOV. 17, 1942. w D NQ 2,302,303

SOLVENT EXTRACTION OF NAPHTHAS Filed April 26, 1941 ZAFF/IVA TE OUTLET COOL/NC v ZONE f SOLVE REaov y ZONE.

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B A I W Patentedfl-Nov. 17, 1942 SOLVENT EXTRACTION OF NAPHTHAS Gordon W. Duncan, Scotch Plains, N. .L, assignor to Standard OilDevelopmentCompany, a corporation of Delaware Application April 26,

5 Claims.

The present invention is concerned with the separation of oils into their relatively more aromatic constituents and into their relatively more parafiinic constituents. The invention is more particularly concerned with the treatment of petroleum oils, especially petroleum oils boiling in the naphtha, kerosene, and gas oil range, with a solvent selected from the class of solvents which have been found to give particularly desirable results. selected from the class of hydroxy polyamines characterized by having an ethylene group be tween the respective nitrogen atoms. The present application is a continuation-in-part of my application No. 286,339, filed July 25, 1939, entitled Solvent extraction of naphthas.

It is known in the art to treat oils, particularly petroleum oils, with various selective solvents in order to segregate the oils into their relatively more parafiinic or hydrogen rich constituents and into their relatively more aromatic or hydrogen poor constituents. In these processes, solvents of the class which have a preferential selectivity for the more aromatic type compounds are usually employed, as for example, phenol, furfural, sulfur dioxide, cresol, nitrobenzene, aniline, beta beta dichlor diethyl ether, and the like. Solvent mixtures of these solvents are employed as well as other substances having the ability to modify the selectivity and solvent power of the particular solvent or solvent mixture. Substances of this type are water, liquefied normally gaseous hydrocarbons such as propane and butane, as well as alcohols and glycols. The oil and the solvent, or solvent mixture, employed are contacted by various methods, as for example, by a batch or by a semi-batch operation. However. the usual method employed is a countercurrent tower treating operation. In this operation, the lighter phase, usually the oil, is introduced at the lower or middle section of a countercurrent treating tower. The heavier phase, usually the solvent, is introduced into the upper part of the countercurrent solvent treating tower. The re spective phases flow countercurrently under conditions in which complete contact between the respective phases is secured. This is usually accomplished by suitable distributing and contact ing means. Temperature and pressure conditions are maintained on the system adapted to secure the formation of a solvent-rich or extract phase and the formation of a relatively solventpoor, or rafiinate phase. The respective phases are removed from the tower and the solvent separated by any suitable means, such as by dis- The solvents of the present invention are 1941, Serial No. 390,446

tillation, washing, and the like. For commercial solvent treating processes it has been diflicult to find a solvent which is entirely suitable in all respects. An ideal solvent is one which will make a clear separation between the aromatic and the paraflinic constituents of the oil and which will also extract substantially the entire quantity of aromatic constituents present. It is also desirable to have the solvent exhibit this preferential selectivity at relatively low temperatures in order to reduce operating difiiculties and expenses. Furthermore, it is desirable that the selective solvent be readily and economically removable from the extract and raffinate phases. The selective solvent is usually separated from the raffinateand extract phases by i e-extracting said phases with a secondary solvent or by distillation. If distillation be employed to separate the solvent from the oil it is necessary that a suificient difference exist with respect to the various boiling points. Solvent recovery from the respective phases, particularly from the extract phase, will be greatly facilitated provided the particular solvent employed is completely miscible with the relatively more aromatic fraction at operating temperature, which temperature should not be excessively above atmospheric temperatures due to heat economies, and providing the solvent tends, toward immiscibility with the extract at 30 temperature not substantially below atmospheric temperatures.

I have now discovered a class of solvents which possess these characteristics and which are therefore particularly desirable in the commercial sol- 35 vent treatment of petroleum'oils. The solvents of my invention are selected from the class of substances known as hydroxy polyamines, characterized by having an ethylene group between the respective nitrogen atoms, and their deriva- 40 tives. Solvents of this class are, for example,

hydroxyethyl ethylene di-amine having a chemical structure as follows:

H2NCH2CHz-l T( JCH3 countercurrent solvent treating tower l by means of feed line 2. The feed oil flows upwardly through tower I and contacts downflowing solvent which is introduced to the tower by means of solvent feed line 3. Water is introduced into the countercurrent treating tower I at a plurality of points by means of lines A, 5, 6 and 1. Temperature and pressure conditions in tower I are adapted to secure the formation of a rafflnate phase and a solvent extract phase. The raffinate phase is withdrawn from tower I by means of line 8, cooled, if desired, in cooler 9 and introduced into separation zone I0. The cooling will, in general, be sufficient to substantially completely separate the solvent from the parafifinic type oil. However, under certain conditions, it may be desirable to add water to separation zone I by means of line I I. The added water will substantially completely remove the remaining solvent and form a water-solvent phase. The water-solvent phase is withdrawn from separation zone I0 by means of line I2, while the solvent-free rafflnate is withdrawn by means of line I3. The solvent extract phase is withdrawn from solvent treating tower I by means of line I4, cooled, in cooler I5, and introduced into separation zone I6. Due to the marked change in solubility of aromatics in hydroxy ethyl ethylene di-amine with a change in temperature,'separation between the solvent and the highly aromatic oil occurs in separation zone IS. The precipitated oil phase may be returned to solvent treating tower I by means of line I1. Under certain conditions, it may be desirable to add water into separation zone I 6 by means of line I8. The extract phase containing solvent is introduced into distillation zone I9 by means of line 20. The highly aromatic petroleum oil is removed overhead from distillation zone I9 by means of line 2| while'the solvent is withdrawn by means of line 22 and recycled to line 3. The overhead from zone I9 comprising oil and steam is passed into separation zone 23. The extract product is removed from separation zone 23 by means of line 24, while the water layer is removed by means of line 25 and recycled to lines l, I0, and I8.

The process of the present invention may be widely varied. The respective zones may comprise any suitable number and arrangement of units. Desirable solvents in the treatment of petroleum oils boiling in the range below about 420 F. have been found to be the hydroxy ethyl di-amines, particularly the high boiling monohydroxy ethyl ethylene di-amines.

Hydroxy ethyl ethylene di-amine is completely miscible with 90% benzol at 115 F. and substant ally completely immiscible with a highly paraffinic fraction boiling in the range from about 250 F. to 400 F. This solvent at room temperatures precipitates a substantial amount of benzol. Thus, any desired solubility of naphtha may be obtained by raising the temperature while the use of reflux by cooling makes it possible to produce practically 100% aromatic extracts. Hydroxyethyl ethylene di-amine is very soluble in water and a benzol-amine solution and immediately upon the addition of water, will form a benzol phase substantially free of solvent and a water-solvent phase. Hydroxy ethyl ethylene diamine has a boiling point of about 470 F. and may, thus, be readily recovered from petroleum oils boiling in the gasoline range by distillation.

The amount of solvent used per volume of oil treated will, in general, depend upon the character of the oil being treated, the conditions of yields desired. In general, it is preferred to employ from about 0.5 to 4 volumes of solvent per volume of oil. Temperature and pressure conditions are likewise adjusted to secure an optimum operation and are a function, to a large extent, of the above enumerated factors. In general, it is preferred to employ atmospheric pressure and to maintain the temperature in the countercurrent treating zone in the range from about 100 F. to about 125 F. It has been found that at these temperatures, the solvent dissolves a maximum amount of the aromatic constituents and a minimum quantity of the paraffin constituents. The amount of water added likewise is adjusted to secure an optimum separation between the aromatic type compounds and the par afiinic type compounds. In general, it is desirable to add from about 5 to about 10% of water based upon the volume of solvent and to add the water at a plurality of points in the countercurrent treating zone. The extent to which the solvent extract phase is cooled will be determined to a large extent by the quality and yield desired. For example, if it be desired to produce an extract comprising substantially 100% aromatic type constituents, it is preferable to cool the solvent extract phase to a temperature of about 70 F.

Although the solvent may be removed from the respective phases by distillation, it is preferred to remove the same by washing with water. It has been found that the solvent will be readily removed from the respective phases by adding from about to about 1.25% of water, based upon the volume of solvent present.

In order to further illustrate the invention, the following example is given which should not be construed as limiting the same in any manner whatsoever:

was treated with of hydroxy ethyl ethylene di-amine. The results secured were as follows:

. 100% batch treats on miarture of 20% toluene- 80% iso-octane Aromatics in extract percent: 7

From the above it is apparent that hydroxy ethyl ethylene di-amine is extremely selective and very desirable. The operating temperature of about F. is in the most desirable range for extracting petroleum oils boiling in the motor fuel boiling range.

What I claim as new and wish to protect by Letters Patent is:

1. Process for the separation of petroleum oils into their relatively more aromatic constituents and into their relatively more paraffinic constituents, comprising extracting said oil with a solvent comprising hydroxy ethyl ethylene di-amine under conditions to form a solvent extract and a raifinate phase, separating the respective phases and removing the solvent therefrom.

2. Process for the separation of petroleum oils boiling below about 400 F. into their relatively more aromatic constituents and into their relatively more parafiinic constituents comprising extracting said oil in the liquid phase with a solvent comprising hydroxy ethyl ethylene di-amine under conditions to form a solvent extract phase and a rafinate phase, separating the respective phases and removing the solvent therefrom.

3. Process in accordance with claim 2 in which said solvent is removed from the respective phases by washing with water.

4. Process for the separation of petroleum oils boiling below about 460 F. into their relatively 10 more aromatic and into their relatively more parafiinic constituents, comprising extracting said oil with a solvent comprising hydroxy ethyl ethylene di-amine under temperature and pres- GORDON W. DUNCAN. 

